Main Group Heterocycles from Lithiated Phosphinimines
Bibliographic record
Abstract
Reaction of the phosphinimines (Me) t Bu 2 PNSiMe 3 ( 1 ), (Me) t Bu 2 PNC 6 H 2 Me 3 ( 3 ), and (PhCH 2 ) t Bu 2 PNSiMe 3 ( 6 ) with n BuLi and subsequently (C 6 F 5 ) 2 BCl affords the four-membered heterocycles [((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNSiMe 3 ] ( 2 ), [((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNC 6 H 2 Me 3 ] ( 5 ), and [((C 6 F 5 ) 2 BCH(Ph)) t- Bu 2 PNSiMe 3 ] ( 7 ), respectively. The related phosphinimine ( i Pr) t Bu 2 PNSiMe 3 ( 8 ) reacts with t BuLi to give (LiCMe 2 ) t Bu 2 PNSiMe 3 ( 9 ), which reacts with (C 6 F 5 ) 2 BCl to yield the five-membered heterocycle [((C 6 F 5 ) 2 BCH 2 CH(Me)) t Bu 2 PNSiMe 3 ] ( 10 ). Similarly, the species [(Me 2 AlCMe 2 ) i Pr 2 PNSiMe 3 ] ( 12 ) and [((Me 2 N) 2 BCMe 2 ) i Pr 2 PNSiMe 3 ] ( 13 ) were prepared from lithiation of the phosphinimine i Pr 3 PNSiMe 3 ( 11 ). In exploring the chemistry of these heterocycles, compound 2 reacts with [Me 3 NH]Cl and MeOH to open the heterocycle, giving [(C 6 F 5 ) 2 B(Cl)CH 2 P t Bu 2 NH(SiMe 3 )] ( 14 ) and ((C 6 F 5 ) 2 B(OMe)CH 2 ) t Bu 2 PNH 2 ( 15 ), respectively. Subsequent treatment of 15 with Me 3 SiCl affords the species ((C 6 F 5 ) 2 B(Cl)CH 2 ) t Bu 2 PNH 2 ( 16 ), while treatment of 16 with n BuLi gives [((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNH)] ( 17 ). Compound 17 coordinates AlMe 3 to give ((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNH](AlMe 3 ) ( 18 ), while 15 reacts with AlMe 3 to give the six-membered heterocycle [((C 6 F 5 ) 2 B(OMe)CH 2 ) t Bu 2 PNH)(AlMe 2 )] ( 19 ). This chemistry is discussed and the implications are considered. X-ray crystallographic data are reported for 2, 5, 7, 9, 10, 14, and 17 .
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.016 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".